Tandem GC/MS: A useful tool for studying end-capping reactions of oligo(styryl)lithium anions

Anionic living polymerization methods, using organometallic initiators such as butyllithium reagents, have proven useful for, inter alia, styrene polymerization and are amenable to subsequent functionalization of poly(styryl)lithium in the termination step. In this study, general methods for the selective preparation of small styrene oligomers and termination of the intermediate oligo(styryl)lithium anions were investigated. The crude reaction mixtures were analyzed directly by tandem gas chromatography/mass spectrometry (GC/MS). Of the carbon- and silicon-based electrophiles tested, chloro(chloroalkyl)silanes, Cl-SiR₂(CH₂)_nCl in particular, were shown by GC/MS to be regioselective end-capping reagents, thus allowing subsequent transformation to the primary amine. The combined GC/MS data allow not only an estimate of the degree of functionalization, but also the identification of by-products, thus providing insight into the end-capping process that otherwise might be difficult to access. © 1995 John Wiley & Sons, Inc.     

CFD evaluation of drop retraction methods for the measurement of interfacial tension of surfactant-laden drops

Drop retraction methods are popular means of measuring the interfacial tension between immiscible polymers. Experiments show that two different drop retraction methods, imbedded fiber retraction (IFR) and deformed drop retraction (DDR), give inconsistent results when a surfactant is present on the surface of the drop. These inconsistencies are deemed to be due to dilution of the surfactant and due to gradients in interfacial concentration of surfactant along the drop surface. This physical picture is quantified for the simple case of a Newtonian drop in a Newtonian matrix, with an insoluble, nondiffusive surfactant at the interface. The drop is deformed in computational fluid dynamics simulations by shearing the matrix, and then allowed to retract. Dilution and interfacial tension gradients effects are found to be especially large at the early stages of retraction, making IFR unsuitable for measuring the interfacial tension of surfactant-laden interfaces. The effects of surfactant dilution and gradients are found to persist even at late stages of retraction, causing the DDR method to underestimate the equilibrium interfacial tension significantly. The largest underestimates occur when the drop viscosity is lower than the matrix viscosity.     

Misting of non-Newtonian liquids in forward roll coating

Misting of liquids in forward roll coating is a problem under certain conditions. The relaxation time is known to influence misting but the fundamental mechanisms are not clear. A new mechanism for misting of dilute non-Newtonian liquids was proposed based on visualizations with a high-speed camera. With these liquids, filaments were created which sometimes transformed into beads-on-string structures and the beads were ejected as mist droplets when the structures broke. Misting was quantified by measuring sizes of the generated droplets, their count and mass concentration. The measurements were related to elasticity of the solutions through their relaxation times. Small levels of elasticity reduce the amount of misting, but higher levels lead to an increase.     

A comparison of boundary element and finite element methods for modeling axisymmetric polymeric drop deformation

A modified boundary element method (BEM) and the DEVSS‐G finite element method (FEM) are applied to model the deformation of a polymeric drop suspended in another fluid subjected to start‐up uniaxial extensional flow. The effects of viscoelasticity, via the Oldroyd‐B differential model, are considered for the drop phase using both FEM and BEM and for both the drop and matrix phases using FEM. Where possible, results are compared with the linear deformation theory. Consistent predictions are obtained among the BEM, FEM, and linear theory for purely Newtonian systems and between FEM and linear theory for fully viscoelastic systems. FEM and BEM predictions for viscoelastic drops in a Newtonian matrix agree very well at short times but differ at longer times, with worst agreement occurring as critical flow strength is approached. This suggests that the dominant computational advantages held by the BEM over the FEM for this and similar problems may diminish or even disappear when the issue of accuracy is appropriately considered. Fully viscoelastic problems, which are only feasible using the FEM formulation, shed new insight on the role of viscoelasticity of the matrix fluid in drop deformation. Copyright © 2001 John Wiley & Sons, Ltd.     

Simultaneous measurement of viscoelastic changes and cell opening during processing of flexible polyurethane foam

A parallel-plate rheomete was constructed and used to study the development of dynamic shear modulus and cell opening under forced adiabatic conditions for a series of flexible slabstock polyurethane foams. Typical industrial formulations were used. The plates were heated to follow the adiabatic temperature profile of a real foam bun during foaming. The rheometer overcomes difficulties encountered in other methods such as heat loss and bubble damage caused by the probe.A four-stage modulus development profile was observed: initial bubble growth, bubble network, polymer stiffening and final curing. Chemical structure development was also studied under forced adiabatic conditions, using Fourier transform infrared spectroscopy. Polymer stiffening coincided with bidentate (hydrogen-bonded) urea formation.The normal force exerted by the expanding foam on the plates was found to be a function of the rate of foam expansion and the foam modulus. A sudden drop in the normal force typically coincides with the visually observed blow-off in the reacting foam bun, thus the normal force profile is a new and accurate indicator of cell opening. The normal force profile clearly shows that cell opening occurs just after the onset of polymer stiffening, thus illustrating the role of polymer rheology in the cell opening mechanism.Dedicated to the memory of Professor Tasos C. PapanastasiouPortions presented at the SPI Polyurethanes Technical/Marketing Conference, October 9–12, 1994, Boston, massachusetts, USA (Best paper award) and at the XIIth International Congress on Rheology, August 18–23, 1996, Québec City, Québec, Canada.